Friday, June 29, 2012

Confined Crystallization of Polyethylene Oxide in Nanolayer Assemblies


We live in an era of increasing reliance on the very small to satisfy humanity’s endless needs and desires for new technologies.  Nanotechnology manifests itself in numerous scientific fields, and polymer chemistry is no exception.  Polymers are generally amorphous, but polymer crystallinity can be observed if the conditions are right.  Semi-crystalline polymer chains (possesses crystalline and amorphous phases) such as polyethylene and nylon are often used as barrier films in food, medicine, and electronics industries.  A barrier is considered highly efficient if small gas molecules are relegated to permeating through only the amorphous regions of the chains (crystalline regions are impenetrable).   Efficiency can be fine-tuned by varying the polymer-film processing conditions to suit the desired amount of crystallinity and chain orientation.  Polymer films can now be made thin enough to effectively confine the crystallization process to 2D; this leads to surprising results. 


Conventionally, confined polymer chains crystallize into lamellae with thicknesses of ~10-20 nm with spherelitic morphology.   However, this convention is skirted at the nanoscale, as isotropic growth is severely hampered to the point of producing lamellar crystal orientation.  This orientation is usually perpendicular to the layer (edge-on), but parallel orientations have been reported several times in the literature; mechanisms for orientation determination remain mysterious for the time being. 
Normally, researchers prepare 2D crystallization of polymers via solution processes such as spin-coating or Langmuir-Blodgett (LB) techniques, but these are limited by the solvent requirement and the small quantity of material fabricated.  LB techniques enable layered nm morphologies due to microphase separation of dissimilar block copolymers within the thin films.  Alas, block copolymers are notoriously difficult to synthesize and align with respect to the direction of the thin films. 

Enter a new technique known as layer-multiplying extrusion.  It uses forced assembly to create alternating layers of two polymers that number up to the 100,000s.  Almost any melt-processable polymer can be formulated into kilometers of nanolayered films with thicknesses of ~10 nm.  With less material comes an explosion of new previously unknown properties (“less is more”). 
The materials used in this study are polyethylene oxide (PEO, also known as polyethylene glycol), which has the following structure:

                                                   HO-CH2-(CH2-O-CH2-)n-CH2-OH
The other is ethylene-co-acrylic acid (EAA), a copolymer with much lower crystallinity than PEO:  
Films with 33, 257, and 1025 alternating EAA and PEO layers were extruded, with various thicknesses and composition ratios, including (EAA/PEO vol/vol) 50/50, 70/30, 80/20, and 90/10.  The nominal PEO layer varied from 3.6 µm to 8 nm. 

The films were subjected to oxygen permeability tests with respect to to layer thickness.  The results are shown below:

Fig. 1 The effect of layer thickness on oxygen permeability. (A) Oxygen permeability of films with equal volume fractions of EAA and PEO. The dashed line indicates P// calculated from Eq. 1. (B) Oxygen permeability of the PEO layers from films of varying composition calculated from Eq. 2. The dashed line indicates PPEO. The open symbol is for a film with PEO layer breakup. The solid lines are drawn to guide the eyes. 
The plots show a significant decrease in O2 permeability.  Gas permeability for layered assemblies is modeled by the following equation. 
     (1)
where ��PEO is the volume fraction of PEO and PPEO and PEAA are the permeabilities of PEO and EAA, respectively.  Upon plugging determined values of PPEO and PEAA from literature into Eq. (1), the result did not agree with the findings reported in the plot above. Eq. (1) predicts increasing permeability with respect to decreasing PEO thickness, but the data show the opposite trend. Eq. (1) was then modified to account for the apparent sensitivity to PPEO due to the far lesser permeability of PEO; it still did not agree with the plotted data with the exception of thicker PEO layers as indicated by the dashed line.  Clearly, the PEO nanolayers possess some previously unknown crystalline morphology that bestowed them with staggeringly low permeability.  However, differential scanning calorimetry revealed that the PEO and EAA layers (even the very thin ones) share the same melting enthalpy and melting temperature as the control films; this means that the changes in crystalline morphology granting the PEO nanolayers low permeability was not accompanied by changes in crystallinity nor lamellar thickness. 


Upon examination by AFM, the authors found that the thin 20 nm PEO layers exhibited single lamellae that extended beyond the field of the AFM image.  The single lamellae are said to be very large single crystals.  Reducing the PEO layer thickness to 8 nm then induces breakage, thereby increasing the permeability.  Fig. 2 below shows the AFM image of the 20 nm PEO layer, and an accompanying schematic showing a gas diffusion pathway through the layered assembly.

Fig. 2  AFM phase images of partial cross sections of the layered EAA/PEO films. The PEO layer has substantially higher crystallinity than the EAA layers and hence appears bright in the AFM images. (A) A low-resolution image of an EEA/PEO film with 50/50 composition, 33 alternating layers, and nominal PEO layer thickness of 3.6 mm. (B) A higher-resolution image showing the spherulitic morphology of the 3.6-mm-thick PEO layer. (C) A low-resolution image of an EAA/PEO film with 70/30 composition, 1025 alternating layers and nominal PEO layer thickness of 110 nm. (D) A higher-resolution image of the 110-nm-thick PEO layers showing the oriented stacks of PEO lamellae. (E) A high-resolution image of an EAA/PEO film with 90/10 composition, 1025 alternating layers, and nominal PEO layer thickness of 20 nm showing that the PEO layers crystallized as single, extremely large lamellae. (F) A schematic showing the gas diffusion pathway through the layered assembly with 20-nm- thick PEO layers. The arrows identify the EAA layers and PEO layers. 
The lamellar crystalline region is considered impermeable, with the lamellar fold surfaces constituting the permeable amorphous regions.  As seen in Fig. 2, the gas pathways depend on the frequency of defects such as lamellar edges.  The permeability is now expressed by



   (2)
 where α is the aspect ratio of the impermeable platelets (length/width), and �� is the volume fraction of impermeable platelets; the platelets are orientated perpendicular to the flux.  For the thinnest PEO layers, the aspect ratio was as high as 120, which meant the lamellae extended up to 2 µm for the 20 nm thick layers.   Gradually thickening the PEO layer relaxed the restrictions on 3D growth, which returned the morphology to spherelitic.   The results were further confirmed by small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS). 

This work is a major breakthrough in polymeric applications for nanotechnology because it shows experiment trumping theory, and possibly describes a major advance for gas-barrier films.  Its importance is amply demonstrated by the 51 citations it has generated since its publication in 2009.  Science Magazine accepted the paper because of its reliance on well-established analytical techniques (AFM, differential scanning calorimetry, SAXS, WAXS), and, more importantly, because of its broad significance in the field of nanoscience. 

This significance is underscored by the novel utilization of a relatively new technique–coextrusion–on readily available polymers to engineer nanolayered polymeric formations in sufficient amounts to allow for probing links between the confined crystalline morphology and the properties exhibited.  This opens up new possibilities for packaging methods, i.e., incorporating polymer nanolayers into common polymeric films for less cost, thereby reducing the environmental and energy consequences.  

Wednesday, June 20, 2012

Laser Ablation: Discussion & Conclusion

Fig. 11 from the last entry does not bode well for laser ablation as a profiling technique for CARCs (chemical agent resistant coatings).  Why?  Because it didn't resolve the UV-damanged region in the topcoat.  At least this was a feasibility study, so its purpose was fulfilled, but a better alternative to ATR-mode FTIR depth profiling still awaits discovery.  Fig. 6 from the last entry shows remarkable resilience from the signature peaks after ablation.  That should mean then ablation shouldn't be a factor when one investigates the coating after QUV exposure (accelerated weatherization under controlled conditions).  Fig. 1 shows why.

Fig. 1 FTIR spectra of major organic and inorganic bands for baseline sample (1), 15-mm-deep transmission-mode spectrum in UV-aged sample (2) and 15-mm-deep ablation window in UV-aged sample (3). 
There shouldn't be discernible differences for spectra (2) and (3), but difference is obvious for the carbonyl peak on the left.  Considering that most CARCs (to my limited knowledge) have polyurethane binders, this can be considered a death blow to the possibility of laser ablation being used as a depth-profiling technique for CARC (chemical agent resistant coating) films after long-term exposure to the elements.  The authors speculate that the ablation process creates ether groups (C–O–C), which overlap with carbonyl groups.

In addition, the amide peaks seen in the spectra of the aged samples likely stem from other functional groups that overlap; they might result from a complex interaction between the aging and ablation processes.  There's still the chance that the original amide II group had reformed after the ablation, which explains the awful ablation profile in Fig. 10(b) of the last blog entry.  This reformation effect was seen in previous studies involving UV-induced cross linking between proteins and DNA with little disruption to the bulk protein chemistry.  This is important considering the chemical similarities between peptide bonds (–CO–NH–) in protein and urethane bonds (–O–CO–NH–) within polyurethane.  

The greater activity within the carbonyl region of Fig. 1 above is perhaps caused by a carboxyl group  (–CO–OH) rather than carbonyl or even ether.  If so, there should be larger peaks in the –OH stretching region (~3300 cm-1), but not so large that it surprises the aged-but-unblated sample.  Alas, Fig. 2 below shows this is not the case.

Fig. 2  FTIR spectra showing (OeH) and (CH2) bands for baseline sample (1), 15-mm-deep transmission-mode spectrum in UV-aged sample (2) and 15-mm-deep ablation window in UV-aged sample (3). 
(3) lies between (2) in the CH2 stretching region (2937 cm-1), but not in the -OH area (3364 cm-1).  They attribute this to another unforeseen reaction with the ablation process.  Nevertheless, it's clear from here that femtosecond laser ablation is unreliable as a depth-profile technique for aged CARC films.